JP2003292816A - Inorganic function-adding agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inorganic function-adding agent which can add an excellent function to a substrate. <P>SOLUTION: This inorganic function-adding agent comprises an inorganic compound whose surface is covered with at least one compound selected from the group consisting of compounds containing silicon, compounds containing aromatic groups and polymers and an average particle size is not less than 1 nm and less than 1,000 nm. The ratio of the particles whose size is not less than 100 nm is not more than 10% of all the particles. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an inorganic functional additive. More specifically, the present invention relates to a function-imparting agent capable of imparting excellent functional properties to substances such as metals, inorganic compounds, organic compounds and polymers.

[0002]

2. Description of the Related Art Plastics such as a thermoplastic resin or a thermosetting resin, rubber, metal or glass have excellent material properties, and are therefore used as automobile materials, home electric appliances materials, and OA.
It is used in various fields such as equipment materials, packaging materials, and building materials. However, in response to the recent demand for high quality or functionality of users, in the case of polymers such as plastics and rubber, surface characteristics such as surface hardness,
There are problems such as flame retardancy, and in the case of metals, there are problems such as corrosion, and the development of a functionality-imparting agent is required as a means for solving them. For example, as a method of improving the functionality of the resin, it is known to add a modifier such as an inorganic compound to the resin, and the properties have been improved to some extent by this, but there is a problem such as deterioration of mechanical properties. Was newly born.

To solve this problem, a resin composition (US Pat. No. 5,391,594) containing a silicone polymer powder composed of silica and polydiorganosiloxane and having an average particle size of 1 to 1000 μm, a thermoplastic resin containing silicone and an inorganic substance is used. A flame-retardant resin composition (JP-A-11-140329) to which a mixture of the above is added, and the average particle size of polydiorganosiloxane gum and silica is 1 to 100.
Resin composition of 0 μm silicone rubber powder and polyphenylene ether (JP-A-5-230362), flame-retardant polyphenylene ether composition comprising polyphenylene ether, liquid polydiorganosiloxane and filler (JP-A-5-262977). Gazette), a polyphenylene ether, a shape anisotropic filler, a phosphoric acid ester flame retardant, and a thermoplastic resin composition comprising a silicone polymer powder composed of polydiorganosiloxane and silica (JP-A-10-46025). There is. However, since the particle size of the inorganic compound used in the above publication is large, flame retardancy, mechanical strength and other functions are not sufficient, and a function-imparting agent having outstanding performance that withstands practical use is required. ing.

[0004]

SUMMARY OF THE INVENTION In view of the above situation, it is an object of the present invention to provide an inorganic function-imparting agent that does not have the above-mentioned problems, that is, enables excellent function-imparting. To do.

[0005]

Means for Solving the Problems As a result of intensive investigations by the present inventors on a modifier capable of imparting excellent functional properties, surprisingly, a specific inorganic compound dramatically improves the function-imparting effect. And completed the present invention. That is, the present invention comprises an inorganic compound surface-coated with one or more compounds selected from a silicon-containing compound, an aromatic group-containing compound, and a polymer, and having an average particle size of 1 nm to 10 nm.
The present invention provides an inorganic function-imparting agent, characterized in that the proportion of particles having a particle diameter of 100 nm or more and less than 00 nm is 10% or less in the total number of particles.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
The (A) function-imparting agent in the present invention is a surface for improving surface properties such as scratch resistance, light resistance, weather resistance, lubricity, slidability, antistatic property and conductivity on resin, metal, glass and the like. Modifier, stabilizer for improving stability against heat, solvent, water and other external stimuli, or paint modifier for improving coating properties by adding to paint, other adhesives, viscosity It has a function as a control agent, a heat ray absorbent, and the like, and is not particularly limited as long as it has a functional property. Use as a flame retardant is particularly preferable.

In the present invention, an excellent function can be imparted by adding (A) to a base material such as (B) polymer, metal or glass. Here, (A) is a silicon-containing compound,
It is an inorganic compound which is surface-coated with at least one compound selected from the group consisting of a compound containing an aromatic group and a polymer. And it is essential that the average particle diameter of (A) is 1 nm or more and less than 1000 nm, preferably 1 to 900 nm, more preferably 1 to 700 nm, most preferably 1 to 500 nm, and very preferably 1 to 100 nm. Is. Further, the particle diameter of (A) is 100
The ratio of particles having a size of nm or more is 10% or less, preferably 8% or less, more preferably 5% or less, based on the total number of particles.
Most preferably, it is 2% or less, and most preferably, it is substantially absent. By satisfying the above requirements,
As a result of improving the dispersibility of (A) in (B), it has been found that the functional properties such as mechanical strength, flame retardancy and extrusion stability are improved, and the present invention has been completed.

Each component of the present invention will be described in detail below. The inorganic compound in the component (A) in the present invention is
Surface coating with the surface treatment agent of the requirements of the present invention, particle diameter is 1
There is no particular limitation as long as the ratio of particles of 00 nm or more and the requirements for the average particle size are satisfied. Examples of the inorganic compound (A) include silicon oxide, aluminum oxide, iron oxide, cesium oxide, zinc oxide, titanium oxide, yttrium oxide, zirconium oxide, tin oxide, copper oxide, magnesium oxide, manganese oxide, molybdenum oxide, molybdenum. Metal oxides such as calcium zincate, zinc molybdate, zinc phosphate, holmium oxide, cobalt blue (CoO ・ Al ₂ O ₃ ) or complex oxides such as Al ₂ O ₃ / MgO, iron, silicon, tungsten, manganese. Examples thereof include metals such as nickel and platinum, nonmetals such as carbon and graphite, and metal carbides such as silicon carbide, boron carbide and zirconium carbide. Among them, metal oxides are preferable, and silicon oxide and aluminum oxide are particularly preferable.

The metal oxide preferred in (A) in the present invention is produced by a liquid phase method or a vapor phase method, and the vapor phase method is preferable from the viewpoint of dispersibility, and US Pat. No. 5,460,701 (corresponding Japanese Patent Publication). 2000-24493). Such metal oxides are sold, for example, by Nanophase Technology Inc. in the US as ultrafine particle nanotechs. Further, a metal molybdate of Sherwin-Williams, USA can also be preferably used.

Among the compounds of (A), silicon oxide is extremely preferable. Silicon oxide is also referred to as synthetic silica, and when roughly classified, there are two synthetic methods, a wet method and a dry method. The former is
There are those synthesized by the reaction of sodium silicate and mineral acid, those by hydrolysis of alkoxysilane, and the like. The latter includes those synthesized by high temperature hydrolysis of silicon halide in an oxyhydrogen flame. Such synthetic silica is preferably amorphous. Amorphous silica of (A) is 60-90 in a mixture of water and alkali metal silicate.
Produced by adding acid at ° C. Water and / or silicate may be heated separately or may be mixed and heated at the same time. The alkali metal silicate is, for example, an alkali metal or alkaline earth metal salt of meta or disilicate, and is not particularly limited. Further, it is preferable to use an electrolyte such as sodium sulfate as a reaction medium.

As another preferable synthetic silica, there is a hydrophilic or hydrophobic fumed silica referred to as fumed silica, and hydrophobic fumed silica is particularly preferable. Such fumed silica is disclosed in
It is manufactured by the method described in JP-A-000-86227, and can be manufactured by a dry method in which silicon tetrachloride and hydrogen, oxygen, and water are used for high-temperature hydrolysis. For example, it is obtained by using a volatile silicon compound as a raw material, and heating and decomposing it in a flame burned by supplying it to a burner together with a mixed gas containing a combustible gas and oxygen at a high temperature of 1000 to 2100 ° C. As the volatile silicon compound as a raw material, for example, a volatile silicon halide compound is preferable,
_{SiH 4, SiCl 4, CH 3} SiCl 3, CH 3 SiHCl 2, HSiCl 3, (CH 3) 2 SiCl 2,
(CH ₃ ) ₃ SiCl, (CH ₃ ) ₂ SiH ₂ , (CH ₃ ) ₃ SiH, alkoxysilanes and the like can be mentioned. The mixed gas containing a combustible gas and oxygen is preferably one capable of producing water, hydrogen, methane, butane, etc. are suitable as the combustible gas, and oxygen, air, etc. are used as the oxygen-containing gas.

The molar ratio of the volatile silicon compound and the mixed gas is such that the molar equivalent of the volatile silicon compound is 1 molar equivalent and the molar equivalent of oxygen in the mixed gas containing oxygen and hydrogen which is a flammable gas is 2.5 to. 3.5 and hydrogen molar equivalents of 1.5-3.
Adjust to the range of 5. Here, the molar equivalents of oxygen and hydrogen refer to stoichiometric equivalents that react with each raw material compound (volatile silicon compound). When a hydrocarbon fuel such as methane is used, it means a molar equivalent in terms of hydrogen. To reduce the average particle size of silica, hydrogen and oxygen are used in excess with respect to 1 mol of the volatile silicon compound, so that the solid (silica) / gas (oxygen, hydrogen) ratio in the reaction mixture is reduced. However, this can be achieved by reducing collisions between solid particles and suppressing particle growth due to melting.

Yet another preferred synthetic silica described above is a synthetic silica manufactured by Nanophase Technology, Inc. manufactured by the above-mentioned vapor phase method. And, one of the preferable synthetic silica is Polyhedral Oligomeric Silsesquioxane (P
OSS) and is manufactured by the organic-inorganic hybrid method. The ratio of particles having a particle diameter of 100 nm or more defined in the present application is determined by the method according to the above-mentioned manufacturing conditions change or 100
There is a method of adding an arbitrary amount of an inorganic compound having a particle size of 100 nm or more to an inorganic compound having no particle size of 100 nm or more.

The surface treatment method of the compound (A) is not particularly limited, but it is preferable to use a surface treatment agent having a functional group capable of reacting or interacting with the inorganic compound. For example, (A) is surface-coated with one or more compounds selected from a silicon-containing compound, an aromatic group-containing compound, especially a compound containing an aromatic group and silicon, and a polymer. For example, in the case of the most preferred synthetic silica as (A), there may be mentioned a method of forming a bond by surface-treating silica with a polymer having a functional group capable of reacting with the silanol group of silica or a silane coupling agent. .

The polymer having a functional group capable of reacting with the silanol group of silica is a functional group in a polymer such as a rubber-like polymer, a thermoplastic resin, or a thermosetting resin described in (B) described later. The polymer itself is not particularly limited, but for example, a polymer having the same or compatibility or interaction with (B) is preferable. Examples of functional groups capable of reacting with silanol groups include epoxy groups, hydroxyl groups, isocyanate groups, ester groups such as maleic acid esters, amino groups, carboxylic acid groups, and maleic acid groups.

One of the preferable surface treatment agents is an epoxy-modified styrene polymer when the styrene polymer is used as (B). As another surface treatment agent capable of reacting with the silanol group of silica, a silane coupling agent and the like can be mentioned. For example, dimethyldichlorosilane treatment, hexamethyldisilazane treatment, octylsilane treatment, methacryloxysilane treatment, aminosilane, hexamethyldisilazane treatment, and dimethylsilicone oil treatment, diphenyldichlorosilane treatment, methylphenyldichlorosilane treatment, hexaphenyldisilazane treatment. processing,
Those treated with phenylalkylsilane, phenylmethacryloxysilane, phenylaminosilane, and phenyl group-containing silicone oil can be preferably used. Among them, diorganosilicone treatment such as dimethylsilicone oil treatment and methylphenylsilicone treatment or dialkyldihalosilane treatment such as dimethyldichlorosilane treatment, aromatic group-containing organosilicone treatment such as diphenylsilicone oil treatment and methylphenylsilicone treatment, or diphenyldiene The aromatic group-containing dihalosilane treatment such as chlorosilane treatment and phenylalkyldichlorosilane silane treatment is most preferable.

The surface treatment is carried out, for example, in Japanese Patent Application Laid-Open No. 9-3100.
No. 27, No. 9-59533, No. 6-87609, the silica is put in a container equipped with a stirrer such as a Henschel mixer, and various surface treatment agents are added while stirring, preferably. It can be performed by spraying and uniformly mixing. When the surface treatment with a polymer is performed, a polymerizable monomer such as styrene is heat-treated or irradiated with a radical initiator or a photosensitizer in the presence of silica to coat the silica surface with a polymer such as polystyrene. . The concrete method is Y.Shirai, Journ
al ofPolymer Science: Part A: Polymer Chemistry, vol.
39, 2157-2163 (2001); N. Tsubokawa, ibid., Vol. 30, 2241-22.
46 (1992).

The POSS manufactured by US Hybrid Plastics Co., Ltd. contains synthetic silica surface-coated with a low molecular weight compound or polymer, for example, alcohol, phenol, amine, chlorosilane, epoxy, ester,
It is surface-coated with various polymers such as fluoroalkyl, halide, isocyanate, methacrylate, acrylate, silicone, nitrile, norborenyl, olefin, phosphine, silane, thiol, and polystyrene. The amount of (A) was 0.
001 to 200 parts by weight, preferably 0.01 to 1
00 parts by weight, more preferably 0.1 to 50 parts by weight, further preferably 0.1 to 20 parts by weight, most preferably 1 to 1
0 parts by weight. The component (B) in the present invention is a polymer such as a rubber-like polymer, a thermoplastic resin, or a thermosetting resin, or a base material such as metal or glass. Among them, the polymer is preferable, and the heat is particularly preferable. Most preferred are plastic resins.

The most preferable thermoplastic resin (B) in the present invention is, for example, a polyaromatic vinyl type, a polycarbonate type, a polyphenylene ether type, a polyolefin type, a polyvinyl chloride type, a polyamide type, a polyester type or a polyphenylene sulfide type. , A polymethacrylate type, or a mixture of two or more types can be used. Polymers containing aromatic groups such as polyaromatic vinyl-based, polycarbonate-based, and polyphenylene ether-based thermoplastic polymers are particularly preferable. Among them, aromatic vinyl polymer alone, aromatic polycarbonate alone, a resin mainly composed of polyphenylene ether or aromatic polycarbonate is very preferable, for example, a blended product of aromatic polycarbonate and aromatic vinyl polymer, or aromatic polycarbonate, Most preferred is a blended product of an aromatic vinyl polymer and polyphenylene ether.

The aromatic polycarbonate used as the component (B) in the present invention can be selected from aromatic homopolycarbonates and aromatic copolycarbonates.
As a production method, a phosgene method in which phosgene is blown into a bifunctional phenol compound in the presence of a caustic alkali and a solvent, or, for example, a transesterification method in which a bifunctional phenol compound and diethyl carbonate are transesterified in the presence of a catalyst Can be mentioned. The aromatic polycarbonate preferably has a viscosity average molecular weight in the range of 10,000 to 100,000. Here, the bifunctional phenol compound is 2,
2'-bis (4-hydroxyphenyl) propane, 2,
2'-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1'-bis (4-hydroxyphenyl) ethane, 2,2'-bis (4- Hydroxyphenyl) butane, 2,2'-bis (4-hydroxy-3,5-diphenyl) butane, 2,2'-bis (4-hydroxy-3,
5-dipropylphenyl) propane, 1,1′-bis (4-hydroxyphenyl) cyclohexane, 1-phenyl-1,1′-bis (4-hydroxyphenyl) ethane and the like, especially 2,2′-bis (4-Hydroxyphenyl) propane [bisphenol A] is preferred. In the present invention, the bifunctional phenol compounds may be used alone or in combination.

The polyaromatic vinyl polymer as the component (B) in the present invention is one or more selected from rubber-modified aromatic vinyl-based resins, rubber-unmodified aromatic vinyl-based resins and aromatic vinyl-based thermoplastic elastomers. Is an aromatic vinyl polymer. The rubber-modified aromatic vinyl-based resin comprises a matrix of the aromatic vinyl-based resin and rubber particles dispersed therein, and the aromatic vinyl-based resin is an aromatic vinyl monomer in the presence of a rubber-like polymer. , And, if desired, a vinyl monomer copolymerizable therewith, and the monomer (or mixture thereof) is subjected to a known bulk polymerization method, bulk suspension polymerization method, solution polymerization method, or emulsion polymerization method, It can be obtained by graft polymerization on a rubber-like polymer.

Examples of such polymers include high impact polystyrene, ABS resin (acrylonitrile-butadiene-styrene copolymer), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), AES resin (acrylonitrile-polymer). Ethylene propylene rubber-styrene copolymer) and the like. Here, the rubbery polymer needs to have a glass transition temperature (Tg) of −30 ° C. or lower, and if it exceeds −30 ° C., impact resistance is lowered. Examples of such rubbery polymers include diene rubbers such as polybutadiene, poly (styrene-butadiene), and poly (acrylonitrile-butadiene), and saturated rubbers obtained by hydrogenating the above diene rubbers, isoprene rubbers, chloroprene rubbers, polyacrylics. Acrylic rubbers such as butyl acid and ethylene-propylene-diene monomer terpolymers (EPDM) can be mentioned, and diene rubbers are particularly preferable.

The aromatic vinyl monomer which is an essential component of the graft-polymerizable monomer mixture to be polymerized in the presence of the above rubbery polymer is, for example, styrene, α-methylstyrene, paramethylstyrene or the like. However, styrene is the most preferable, but the above-mentioned other aromatic vinyl monomer may be copolymerized mainly with styrene. If necessary, one or more monomer components copolymerizable with the aromatic vinyl monomer can be introduced as a component of the rubber-modified aromatic vinyl resin in (B). When it is necessary to enhance oil resistance, unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile can be used.

When it is necessary to reduce the melt viscosity at the time of blending, an acrylate ester having an alkyl group having 1 to 8 carbon atoms can be used. Furthermore, when it is necessary to further increase the heat resistance of the resin composition, α-methylstyrene, acrylic acid, methacrylic acid,
Monomers such as maleic anhydride and N-substituted maleimide may be copolymerized. The content of the vinyl monomer copolymerizable with the vinyl aromatic monomer in the monomer mixture is 0-40.
% By weight. The rubber-like polymer in the rubber-modified aromatic vinyl resin is preferably 5 to 80% by weight, particularly preferably 10 to 50% by weight, and the graft-polymerizable monomer mixture is preferably 95 to 20% by weight. Preferably 9
It is in the range of 0 to 50% by weight. Within this range, the balance between impact resistance and rigidity of the desired resin composition is improved. Further, the rubber particle size of the styrene polymer is 0.1
To 5.0 μm is preferable, and 0.2 to 3.0 μm is particularly preferable. Within the above range, impact resistance is particularly improved.

The reduced viscosity ηsp / c (0.5 g / d) of the resin portion, which is a measure of the molecular weight of the rubber-modified aromatic vinyl resin.
1, 30 ° C measurement: toluene solution when the matrix resin is polystyrene, methyl ethyl ketone when the matrix resin is unsaturated nitrile-aromatic vinyl copolymer)
Is preferably in the range of 0.30 to 0.80 dl / g, and more preferably in the range of 0.40 to 0.60 dl / g. Reduced viscosity η of rubber modified styrene resin
As means for satisfying the above requirements regarding sp / c, adjustment of the amount of polymerization initiator, polymerization temperature, amount of chain transfer agent and the like can be mentioned.

As a method for producing the rubber-modified aromatic vinyl resin, in particular, a homogeneous stock solution of a rubber-like polymer, a monomer (or a mixture of monomers), and a polymerization solvent is continuously stirred with a stirrer. A bulk polymerization method in which it is fed to a multistage bulk polymerization reactor and continuously polymerized and devolatilized is preferable. When a rubber-modified styrene polymer is produced by the bulk polymerization method, the reduced viscosity ηs
The p / c can be controlled by the polymerization temperature, the type and amount of the initiator, the solvent, and the amount of the chain transfer agent. When a monomer mixture is used, the copolymer composition can be controlled by adjusting the charged monomer composition. The rubber particle size can be controlled by the number of stirring rotations. That is, the particle size can be reduced by increasing the rotation speed and the particle size can be reduced by decreasing the rotation speed.

The aromatic vinyl type thermoplastic elastomer as (B) used in the present invention is a block copolymer comprising an aromatic vinyl unit and a conjugated diene unit, or the conjugated diene unit portion is partially hydrogenated. Is a block copolymer obtained from the above. The aromatic vinyl monomer constituting the block copolymer is, for example, styrene or α-
Methyl styrene, paramethyl styrene, p-chlorostyrene, p-bromostyrene, 2,4,5-tribromostyrene and the like, and styrene is the most preferable, but styrene is the main component and other aromatic vinyl monomers are added. You may copolymerize.

Examples of the conjugated diene monomer which constitutes the above block copolymer include 1,3-butadiene and isoprene. In the block structure of the block copolymer, a polymer block composed of an aromatic vinyl unit is represented by S, and a polymer block composed of a conjugated diene and / or its partially hydrogenated unit is represented by B. In this case, SB, S (BS) n, (where n is 1 to 3)
, S (BSB) n, (where n is an integer of 1 to 2) linear-block copolymer, or (SB) nX.
(However, n is an integer of 3 to 6. X is a residue of a coupling agent such as silicon tetrachloride, tin tetrachloride, and a polyepoxy compound.)
The star shape with the B part as the bond center
It is preferably a block copolymer. Above all, SB
2 type, SBS type 3 and SBBS type 4 linear-block copolymers are preferred.

In the present invention, one of the polyphenylene ethers as the component (B) is a homopolymer and / or copolymer having an aromatic ring in the main chain, which are linked by an ether bond, and specifically, , Poly (2,6-dimethyl-1,4
-Phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, and the like, among which poly (2,6-dimethyl-1,4-phenylene ether) is preferable. The method for producing such a polyphenylene ether is not particularly limited, and for example, a complex of a cuprous salt and an amine according to the method described in US Pat. No. 3,306,874 is used as a catalyst, and, for example, 2,6-xylenol is used. It can be easily produced by oxidative polymerization of propylene.
06,875, U.S. Pat. No. 3,257,357.
U.S. Pat. No. 3,257,358, Japanese Patent Publication No. 52-17880, and Japanese Patent Laid-Open No. 50-5119.
It can be easily manufactured by the method described in Japanese Patent Publication No. Reduced viscosity ηs of the polyphenylene ether used in the present invention
p / c (0.5 g / dl, chloroform solution, measured at 30 ° C.) is preferably in the range of 0.20 to 0.70 dl / g, and is in the range of 0.30 to 0.60 dl / g. Is more preferable. Examples of means for satisfying the above requirements regarding the reduced viscosity ηsp / c of the polyphenylene ether include adjustment of the catalyst amount in the production of the polyphenylene ether.

In the present invention, other function-imparting agent (C) may be used in combination with the (A) function-imparting agent of the present invention, if necessary. At that time, it is preferable to carry other function-imparting agents on the function-imparting agent of the present invention. Among the other function-imparting agents (C), in order to further improve the flame retardancy, a flame retardant (C-1) can be added as required, and sulfur-based, phosphorus-based, nitrogen-based, inorganic It is a flame retardant, a halogen flame retardant, or a fibrous flame retardant.

The sulfur-based flame retardant as the above (C-1) is
For example, potassium trichlorobenzenesulfonate, potassium perfluorobutanesulfonate, potassium diphenylsulfone-3-sulfonate and other organic sulfonic acid metal salts, aromatic sulfonimide metal salts, or styrene-based polymers, aromatics such as polyphenylene ether Polystyrene sulfonic acid alkali metal salt in which a sulfonic acid metal salt, a sulfuric acid metal salt, a phosphoric acid metal salt, a boric acid metal salt or an ammonium salt or a phosphonium salt of the above acid is bonded to the aromatic ring of the group-containing polymer, etc. Is a sulfur-based flame retardant. Such a sulfur-based flame retardant promotes a decarboxylation reaction at the time of combustion to improve flame retardancy, particularly when polycarbonate is used as a polymer. Further, in the case of polystyrene sulfonic acid alkali metal salt, the metal sulfonic acid salt itself becomes a cross-linking point during combustion and greatly contributes to the formation of a carbonized film.

The phosphorus-based flame retardant as (C-1) is
Examples include organic phosphorus-based, red phosphorus-based, and inorganic phosphorus-based flame retardants. Examples of the organic phosphorus flame retardant include phosphine,
Phosphine oxide, biphosphine, phosphonium salt,
Examples include phosphinic acid salts, phosphoric acid esters, and phosphorous acid esters. More specifically, triphenyl phosphate, methyl neobenthyl phosphite, hentaerythritol diethyl diphosphite, methyl neopentyl phosphate, phenyl neopentyl phosphate, pentaerythritol diphenyl diphosphate, dicyclopentyl hypophosphite. , Dineopentyl hypophosphite, phenylpyrocatechol phosphite, ethylpyrocatechol phosphate, dipyrocatechol hypophosphite.

Here, as the organic phosphorus compound, an aromatic phosphoric acid ester monomer and an aromatic phosphoric acid ester condensate are particularly preferable. In the above (C-1), the red phosphorus, which is one of the phosphorus-based flame retardants, is selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide on the surface thereof in addition to general red phosphorus. Those coated with a metal hydroxide coating, aluminum hydroxide, magnesium hydroxide, zinc hydroxide, those coated with a metal hydroxide selected from titanium hydroxide and a thermosetting resin, For example, a coating of a metal hydroxide selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide is double-coated with a coating of a thermosetting resin.

In the above (C-1), the inorganic phosphorus-based flame retardant, which is one of the phosphorus-based flame retardants, is ammonium polyphosphate or a composite flame retardant of it and a nitrogen compound, or a phosphazene-based compound, particularly an aromatic group. It is preferable that the compound has a structure in which a phosphorus atom and a nitrogen atom are bonded by a double bond, and examples thereof include cyclic phosphazene and linear phosphazene. Among phosphazenes, from the viewpoint of compatibility with aromatic polycarbonate, it contains an aromatic group such as a phenyl group, a cresyl group, a xylyl group, and a bisphenyl group as a substituent. Specifically, phenoxypropoxyphosphazene, diphenoxyphosphazene, phenoxyaminophosphazene,
Such as phenoxyfluoroalkylphosphazene,
These phosphazene compounds are produced by substituting chlorophosphazenes with alcohols or phenols.

The nitrogen-based flame retardant as the above (C-1) is
A compound containing a triazine skeleton is typical, and is a component for further improving the flame retardancy as a flame retardant aid for a phosphorus-based flame retardant. Specific examples thereof include melamine, melam, melem, melon (a product of deammonification of 3 molecules of melem at 600 ° C. or higher), melamine cyanurate, melamine phosphate, succinoguanamine, adipoguanamine, and methylglum. Talog anamin, melamine resin, B
Although T resin can be mentioned, melamine cyanurate is particularly preferable from the viewpoint of low volatility.

The inorganic flame retardant as (C-1) is silica, aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, basic magnesium carbonate, or hydroxide. Zirconium, hydrates of inorganic metal compounds such as hydrates of tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide. , Tin oxide, antimony oxide, nickel oxide, copper oxide, metal oxides such as tungsten oxide, aluminum, iron, titanium, manganese, zinc, molybdenum,
Metal powders of cobalt, bismuth, chromium, nickel, copper, tungsten, tin, antimony, etc., and zinc borate, zinc metaborate, barium metaborate, zinc carbonate,
Examples thereof include magnesium carbonate, calcium carbonate, barium carbonate and the like. These may be used alone or in combination of two or more. Among them, those selected from the group consisting of magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate and hydrotalcite have a good flame retarding effect and are economically advantageous.

In the present invention, the fibrous flame retardant used as (C-1) is a fiber in a broad sense including an anisotropic filler including a plate-shaped filler, and is not particularly limited. The average fiber diameter of the fibrous flame retardant is 0.01 to 1
000 μm, preferably 0.1 to 500 μm, more preferably 1 to 100 μm, and most preferably 5 to 50 μm.
μm, and the aspect ratio (length / diameter) is 2 to 1
It is 0000, preferably 50 to 500, more preferably 50 to 300, and most preferably 100 to 200. Further, specific examples of the fibrous flame retardant, cotton, silk, wool, natural fibers such as hemp, rayon, recycled fibers such as cupra, acetate, semi-synthetic fibers such as Promix, polyester, polyacrylonitrile, polyamide, aramid, Polyolefin, carbon, synthetic fiber such as vinyl, glass, inorganic fiber such as asbestos, fiber such as metal fiber or plate-shaped talc, filler such as kaolin or viscous compound, especially aramid fiber, polyacrylonitrile fiber, glass fiber Is preferred.

In the present invention, as other function-imparting agents, aliphatic hydrocarbons, higher fatty acids, higher fatty acid esters, higher fatty acid amides, higher fatty alcohols, metal soaps, organosiloxane waxes, polyolefin waxes, if necessary. Further, one or more kinds of release agents selected from polycaprolactone or a processing aid as a fluidity improver can be blended. In the present invention,
When light resistance is required, as other functionalizing agent, if necessary, an ultraviolet absorber, a hindered amine light stabilizer, an antioxidant, an active species scavenger, a light shielding agent, a metal deactivator, Alternatively, one or more light resistance improvers selected from quenchers may be blended. In the present invention, (C) is 0.00 relative to 100 parts by weight of (B).
1 to 100 parts by weight is preferable, and 0.1 to 100 parts by weight is more preferable.
50 parts by weight, most preferably 1 to 20 parts by weight. In the present invention, the following may be mentioned as examples of particularly preferable embodiments.

The inorganic compound (A) is preferably silicon oxide SiO ₂ having a primary particle size of 10 to 100 nm, especially 10 to 50 nm, and the surface thereof contains a silicon-containing compound, a compound containing an aromatic group, and a heavy compound. It is coated with one or more compounds selected from coalescence. At that time, it is preferable that the coating is not performed by physical adsorption but by a strong bond such as a covalent bond. Specific examples of the surface coating include styrene-based polymer treatment containing active halogen or epoxy group, dimethyldichlorosilane treatment, hexamethyldisilazane treatment, octylsilane treatment, methacryloxysilane treatment, aminosilane, hexamethyldisilazane treatment. Those treated with dimethyl silicone oil, diphenyldichlorosilane, methylphenyldichlorosilane, hexaphenyldisilazane, phenylalkylsilane, phenylmethacryloxysilane, phenylaminosilane, and phenyl group-containing silicone oil are preferred. Can be used for.
Among them, dimethyl silicone oil treatment, methylphenyl silicone treatment, dimethyldichlorosilane treatment, diphenylsilicone oil treatment, methylphenylsilicone treatment, diphenyldichlorosilane treatment, phenylalkyldichlorosilanesilane treatment, among others, styrene containing active halogen or epoxy group Polymer treatment,
Dimethyldichlorosilane treatment, hexamethyldisilazane treatment, dimethyl silicone oil treatment, and methylphenyldichlorosilane treatment are particularly preferable. The treatment amount is 0.0001 to 10,000 with respect to 100 parts by weight of silicon oxide.
Parts by weight, more preferably 0.01 to 1000 parts by weight, most preferably 0.1 to 100 parts by weight.

As the inorganic compound other than silicon oxide as (A), Al ₂ O ₃ , CeO ₂ , TiO ₂ , Y ₂ O ₃ , ZnO, ZrO ₂ , SnO ₂ , CuO, Fe ₂
O ₃ ,, MgO, Mn ₃ O ₄ ,, Ho ₂ O ₃ ,, Al ₂ O ₃ / MgO, ZnMoO ₄ ,, MgO ₄ SiO ₂ ,, CaMoO
₄ , CaCO ₃ and Zn ₃ (PO ₄ ) ₂ are mentioned, and it is preferable to coat the surface with the same surface treatment agent as described above. Excellent flame retardancy is exhibited by adding (A) to the polymer, and as the polymer at that time, bisphenol A type polycarbonate (PC), nylon 6 (PA6), polyethylene terephthalate (PET), polybutylene Terephthalate (P
BT), polytetramethylene terephthalate (PT
T), rubber modified polystyrene (HIPS), ABS resin (ABS), styrene-ethylene-butylene-styrene copolymer (SEBS), maleic anhydride modified SEBS
(M-SEBS), styrene-butadiene copolymer (S
B), polyphenylene ether (PPE), polypropylene (PP), ethylene-octene copolymer (EO),
EO-PP crosslinked product [TPV: EO / PP = 50/50
It is a thermoplastic polypropylene dynamically crosslinked by a twin-screw extruder using (by weight) an organic peroxide and triallyl isocyanurate. ], And especially PC, PP
Polymer alloys obtained by E, HIPS alone or a combination thereof are preferable, and P is extremely preferable.
It is a polymer alloy of C alone or PC and other polymers. For example, PC / ABS, PC / HIPS, PC / PBT, PC / TPV, P
C / SEBS, PC / M-SEBS, PC / PPE, PC / PPE / HIPS.

The composition ratio of the above polymer alloy is PC100.
With respect to parts by weight, other polymers are 0.001 to 100
00 parts by weight, preferably 0.1 to 100 parts by weight, very preferably 1 to 50 parts by weight. When higher flame retardancy is required, it can be achieved by using the following flame retardant together. For example, in the case of PC alone or a polymer alloy mainly composed of PC as a polymer, the following S
By using F alone or SF and PTFE in combination, extremely excellent flame retardancy is exhibited. The above SF and / or PT
The amount of FE added is preferably 0.001 to 100 parts by weight, more preferably 0.0 to 100 parts by weight of the polymer.
1 to 10 parts by weight, and very preferably 0.01 to 1 part by weight.

(1) Organic sulfonic acid metal salt manufactured by Dainippon Ink and Chemicals, Inc., potassium perfluorobutane sulfonate (referred to as SF) (2) bisphenol A bis (diphenyl phosphate) manufactured by Daihachi Chemical Co., Ltd. , [Trade name CR741 (referred to as P1)] (3) 1,3-phenylene bis (diphenyl phosphate) manufactured by Daihachi Chemical Industry Co., Ltd., aromatic condensed phosphate ester derived from resorcin [trade name CR733S (referred to as P2) )] (4) 1,3-phenylene bis (dixylyl phosphate) manufactured by Daihachi Chemical Industry Co., Ltd., [trade name PX200 (referred to as P3)] (5) manufactured by Akarin Phosphorus Chemical Industry Co., Ltd. Name Nova Excel (P4
Called))]

(6) Ammonium polyphosphate manufactured by Chisso Co., Ltd., [trade name: Terrage (referred to as P5)] (7) Phenoxyphosphazene (P6) (8) Magnesium hydroxide manufactured by Kyowa Chemical Industry Co., Ltd. Name Kisuma (referred to as MOH) (9) Melamine Cyanurate Nissan Chemical Co., Ltd. [trade name MC610 (referred to as M1)] (10) Polytetrafluoroethylene Daikin Industries Co., Ltd. (referred to as PTFE) The most preferable combination of the present invention is a combination of the most preferable components of each component, but extremely excellent properties are exhibited even when at least the most preferable components are contained.

The composition obtained by adding the function-imparting agent of the present invention can be manufactured by using a Banbury mixer, a kneader, a single-screw extruder, a twin-screw extruder, which are used in the production of ordinary resin compositions and rubber compositions. Although a general method such as a machine can be adopted, a twin-screw extruder is preferably used. In the twin-screw extruder, (A) and (B), and optionally (C) are uniformly and finely dispersed, and other components are added to continuously add the composition of the present invention. To manufacture,
More suitable.

The composition of the present invention may be prepared by first preparing (A) dispersed in (B) in an average particle size of the requirement of the present application in advance, and then melt-extruding it using it (or While simultaneously melt-extruding A) and (B),
(A) may be produced by simultaneously reaching the average particle of the requirements of the present application, and the production method is not particularly limited. A particularly preferable melt extrusion method has a length L in the die direction with the raw material addition section as a base point, and L / D is 5 to 100.
(Where D is the barrel diameter) when a twin-screw extruder is used. The twin-screw extruder has a plurality of supply parts of a main feed part and a side feed part which are different in distance from the tip part, and between the plurality of supply parts and between the tip part and the tip part. It is preferable that the kneading portion has a kneading portion between the feeding portion and the feeding portion at a short distance from and the length of the kneading portion is 3D to 10D, respectively.

The composition thus obtained can be manufactured into various molded articles by any molding method. Injection molding, extrusion molding, compression molding, blow molding, calender molding, foam molding and the like are preferably used. In the present invention, by molding or processing (A), flame retardancy, dispersibility, oil absorption,
Functions can be imparted to various materials such as stability. The above-mentioned function-imparting agent can impart a function such as a polymer material as a kind of masterbatch.

[0047]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, in these Examples and Comparative Examples, the test methods used for evaluation of various physical properties are as follows. (1) Average particle size of inorganic function-imparting agent The particle size of the inorganic function-imparting agent is calculated by the following method for each particle of 500 inorganic function-imparting agents in a transmission electron micrograph dispersed in water. It is obtained by doing. That is, for the particle size of each particle, the area S of each particle is calculated, and S is used to calculate
Let (4S / π) ^{0.5 be} the particle size of each particle, and calculate the average particle size by number average. The ratio of particles having a particle diameter of 100 nm or more is such that the particle diameter is 100 nm in all the above particles.
The ratio of the above particles was calculated.

(2) Flame retardant VB (Vertical Bur) compliant with UL-94
self-extinguishing property is evaluated by the Ning method. (1
/ 8 inch thickness test piece) ◎: Self-extinguishing property in less than 20 seconds ○: Self-extinguishing property in 20 or more and less than 40 seconds △: Self-extinguishing property in 40 seconds or more ×: Burnt out

(3) Extrusion Stability (Quality Stability) Using a melt extruder, the resin composition was continuously melt extruded for 10 hours, and the Izod impact strength of the obtained composition was measured every hour. Continuous productivity (stability of quality) is evaluated from the rate of change (%) with respect to the average strength. However, the Izod impact strength is measured by a method according to ASTM-D256. (23 ° C., 1/8 inch thickness test piece with V notch) (4) Scratch resistance The tip is a rectangle with a length of 10 mm and a width of 1 mm and a weight of 80.
A 0 g wedge is dropped onto the molded body from a height of 10 cm, and a scratch on the molded body is scanned with a laser beam to measure the scratch depth. The larger the value, the poorer the scratch resistance.

The following components are used as the components used in Examples and Comparative Examples. (B) Function-imparting agent By the method described in JP-A-2000-86227,
It was synthesized by high-temperature hydrolysis of silicon tetrachloride in an oxyhydrogen flame to produce silica having different average particle sizes. Specifically, 1.0 molar equivalent of silicon tetrachloride is supplied to a burner together with a mixed gas of oxygen and hydrogen preheated to 60 ° C. (oxygen 2.69 molar equivalent, hydrogen 1.60 molar equivalent) to burn ( 1
(600 ° C.) to produce fine particle silica. The average particle size is controlled by changing the molar equivalent ratio of oxygen and hydrogen to 1.0 molar equivalent of silicon tetrachloride. Metal oxides other than silica are produced by the vapor phase method disclosed in US Pat. No. 5,460,701 (corresponding Japanese Patent Publication No. 2000-24493).

Then, the surface was coated with various surface treating agents. The surface treatment method is, for example, JP-A-9-310027,
The method described in JP-A-9-59533 and JP-A-6-87609 is used. For example, after putting the silica in a closed Henschel mixer and replacing the inside of the container with nitrogen gas, various treating agents are added to silica while stirring. 20 parts by weight is spray mixed. Then, continue heating and stirring at 250 ° C for 30 minutes,
Cool to room temperature to produce surface treated silica. When the surface is coated with dimethyl silicone, polyether-modified dimethyl silicone (Shin-Etsu Chemical Co., Ltd., trade name: KF
618) is used. Similarly, dimethyldichlorosilane treatment, hexamethyldisilazane treatment, methacryloxysilane treatment, diphenyldichlorosilane treatment, and methylphenyldichlorosilane treatment are performed. When the surface is coated with a polymer, the polymerizable monomer is added to Y. Shirai, Journal of Po
lymer Science: Part A: Polymer Chemistry, vol.39, 2157
-2163 (2001); N. Tsubokawa, ibid., Vol. 30, 2241-2246 (199
Graft polymerization is carried out by the method disclosed in 2). For other surface coatings, see Hybrid P
Polyhedral Oligomeric Silse manufactured by lastics
Use squioxane (POSS). Various inorganic compounds described above are shown in Tables 1 to 3.

(B) Polymer Abbreviated in parentheses as follows. Bisphenol A type polycarbonate (PC), nylon 6 (PA6), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytetramethylene terephthalate (PTT), rubber modified polystyrene (HIPS),
ABS resin (ABS), styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-butadiene copolymer (SB), polyphenylene ether (PP
E), polypropylene (PP), ethylene-octene copolymer (EO), EO-PP cross-linked product (TPV) where TPV is EO / PP = 50/50 (weight ratio)
It is a thermoplastic polypropylene dynamically cross-linked in a twin-screw extruder using organic peroxide and triallyl isocyanurate.

(C) Other function-imparting agents (flame retardants) (1) Organic sulfonic acid metal salt manufactured by Dainippon Ink and Chemicals, Inc., potassium perfluorobutane sulfonate (referred to as SF) (2) polytetrafluoro Ethylene Daikin Industries, Ltd., (referred to as PTFE) Examples 1 to 20 and Comparative Examples 1 to 3 A Henschel mixer was used to mix the compositions shown in Tables 1 to 3, and subsequently an injection port was provided at the center of the barrel. Using the provided twin-screw extruder (40 mmφ, L / D = 47), continuous melt extrusion is performed at a temperature condition of 250 ° C. for 10 hours. As the screw, a double thread screw having a kneading section before and after the injection port is used. A molded body is produced from the composition thus obtained by injection molding at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C., and evaluation is performed. The results are shown in Tables 1 to 3.

[0054]

[Table 1]

[0055]

[Table 2]

[0056]

[Table 3]

[0057]

INDUSTRIAL APPLICABILITY The inorganic function-imparting agent of the present invention can impart excellent functions such as flame retardancy to a base material such as a polymer. The composition obtained by adding the inorganic functionalizing agent of the present invention to a polymer is a VTR, a distribution board, a television, an audio player, a condenser, a household outlet, a radio cassette player, a video cassette, a video disc player, an air conditioner, a humidifier. , Electric home appliances such as electric hot air machines, chassis or parts, CD-ROM mainframe (mechanical chassis), printer, fax, PPC, CR
T, word processor copying machine, electronic cash register, office computer system, floppy disk drive, keyboard, type, ECR, calculator, toner cartridge, OA equipment housing such as telephone, chassis or parts, connector, coil bobbin, Switches, relays, relay sockets, LEDs, variable capacitors, AC adaptors, FBT high-voltage bobbins, FBT cases, IFT coil bobbins, jacks, volume shafts, motor parts, and other electronic and electrical materials, and instrument panels, radiator grills, clusters, Suitable for automotive materials such as speaker grills, louvers, console boxes, defroster garnishes, ornaments, fuse boxes, relay cases, connector shift tapes, etc. Plays role is large.

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Claims (7)

[Claims] 1. A silicon-containing compound, a compound containing an aromatic group, and an inorganic compound surface-coated with at least one compound selected from polymers, and having an average particle diameter of 1 n.
m or more and less than 1000 nm and a particle diameter of 100
An inorganic function-imparting agent, characterized in that the proportion of particles having a size of nm or more is 10% or less in the total number of particles. 2. The inorganic function-imparting agent according to claim 1, wherein the inorganic function-imparting agent is a flame retardant. 3. The inorganic function-imparting agent according to claim 1 or 2, wherein the compound containing an aromatic group is a polyorganosiloxane containing an aromatic group. 4. The inorganic function-imparting agent according to claim 1, wherein the inorganic compound is a metal oxide. 5. The inorganic function-imparting agent according to claim 4, wherein the metal oxide is at least one selected from the group consisting of silicon oxide and aluminum oxide. 6. The inorganic function-imparting agent according to claim 1, which carries a function-imparting agent other than those described in claim 1. 7. A polymer composition comprising the inorganic function-imparting agent according to claim 1 and a polymer.